A covalently functionalized fullerene comprising an electron donating aniline group coupled to the fullerene unit by a saturated heterocyclic bridge is shown to undergo a photoinduced intramolecular electron transfer process that causes quenching of the fluorescence of the adduct and strong decrease of triplet population in polar solvents. VIS-absorption, fluorescence and phosphorescence at 77 K, triplet-triplet absorption, time resolved fluorescence, and redox potentials of the fullerene adduct are presented. Analysis of the solvent dependence of the energetics of the intramolecular electron transfer is given and is in good agreement with the experimental results.